Fluorine-containing maleate, fluorine-containing fumarate, fluorine-containing copolymer and stainproofing agent

ABSTRACT

(1) A perfluoroalkyl diester of maleic acid or fumaric acid, 
     (2) a copolymer obtained by polymerizing the perfluoroalkyl ester, a lower alkyl (meth)acrylate and, if necessary, styrene, and 
     (3) a stainproofing agent comprising the copolymer 
     give excellent water repellency, oil repellency and stainproof properties which have never been heretofore obtained.

FIELD OF THE INVENTION

The present invention relates to a fluorine-containing maleate, afluorine-containing fumarate, a fluorine-containing copolymer and astainproofing agent.

RELATED ART

In order to impart water- and oil-repellency and stainproof propertiesto textile products (e.g. carpet, etc.), various stainproofing agentshave hitherto been suggested.

Japanese Patent Kokoku Publication No. 8606/1973 discloses thatstainproof properties are imparted by treating a fabric with ahomopolymer obtained by polymerizing an ester of an unsaturatedcarboxylic acid having a perfluoroalkyl group at both ends. However,this homopolymer is insufficient in stainproof properties.

Japanese Patent Kokoku Publication No. 37670/1976 discloses thatstainproof properties are imparted to fibers by treating the fibers witha polymer obtained by polymerizing (i) an ester of maleic or fumaricacid having a perfluoroalkyl group at one end and an aliphatic oraromatic group having no fluorine atom at the other end with (ii) theother polymerizable unsaturated compound. Since one end of the ester ofmaleic or fumaric acid has no fluorine atom, its polymerizablity isgood. However, this polymer is insufficient in water- and oil-repellencyand is also insufficient in stainproof properties.

U.S. Pat. No. 3,594,353 discloses that a water repellency and stainproofproperties to oil are imparted to fibers by treating the fibers with apolymer obtained by homopolymerizing an ester of itaconic acid having aperfluoroalkyl group at both ends or one end or copolymerizing saidester with the other polymerizable unsaturated compound. However, thispolymer is insufficient in water- and oil-repellency and stainproofproperties.

Japanese Patent Kokai Publication No. 105723/1993 discloses that awater- and oil-repellency is imparted to fibers by treating the fiberswith a polymer obtained by copolymerizing a fumarate ester having abulky branched alkyl group at one end and a perfluoroalkyl group at theother end with the other copolymerizable unsaturated compound. However,this copolymer is insufficient in water- and oil-repellency andstainproof properties.

None of stainproofing agents which have hitherto been proposed presentlyhas sufficient water- and oil-repellency and stainproof properties.

SUMMARY OF THE INVENTION

A first object of the present invention is to provide a stainproofingagent having sufficient water- and oil-repellency and stainproofproperties.

A second object of the present invention is to provide a polymerconstituting the stainproofing agent.

A third object of the present invention is to provide a monomer whichaffords said polymer.

The present invention provides a stainproofing agent comprising afluorine-containing copolymer, in which said fluorine-containingcopolymer comprises:

(A) at least one repeating unit derived from a monomer which is selectedfrom the group consisting of an OH-- and fluorine-containing maleate

represented by the formula: ##STR1## wherein Rf is a perfluoroalkylgroup having 3 to 21 carbon atoms!, an OH-- and fluorine-containingfumarate represented by the formula: ##STR2## wherein Rf is aperfluoroalkyl group having 3 to 21 carbon atoms!, a fluorine-containingmaleate represented by the formula: ##STR3## wherein Rf is aperfluoroalkyl group having 3 to 21 carbon atoms, and A is an alkylenegroup having 1 to 4 carbon atoms or ##STR4## (wherein R¹ is a hydrogenatom or an alkyl group having 1 to 4 carbon atoms, and R² is an alkylenegroup having 1 to 4 carbon atoms)!, and a fluorine-containing fumaraterepresented by the formula: ##STR5## wherein Rf is a perfluoroalkylgroup having 3 to 21 carbon atoms, and A is an alkylene group having 1to 4 carbon atoms or ##STR6## (wherein R¹ is a hydrogen atom or an alkylgroup having 1 to 4 carbon atoms, and R² is an alkylene group having 1to 4 carbon atoms)!, and

(B) at least one repeating unit derived from an alkyl (meth)acrylatewhose alkyl group has 1 to 6 carbon atoms. (Meth)acrylate means acrylateor methacrylate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an IR chart of the product obtained in Synthesis Example 1.

FIG. 2 is an IR chart of the product obtained in Synthesis Example 2.

DETAILED DESCRIPTION OF THE INVENTION

In the copolymer of the present invention, the repeating unit (A) may bethe above fluorine-containing maleate or fumarate which has an OH groupor no OH group. It is preferred that the repeating unit (A) has the OHgroup. The reason why it is preferred to have the OH group is not clear,but it is assumed that properties of adhesion to a substrate areimproved by having the OH group, thereby improving the stainproofproperties and oil repellency.

The present invention provides a stainproofing agent comprising afluorine-containing copolymer, said fluorine-containing copolymercomprising:

(A) at least one repeating unit derived from an OH-- andfluorine-containing maleate represented by the formula: ##STR7## whereinRf is a perfluoroalkyl group having 3 to 21 carbon atoms!, or afluorine-containing maleate represented by the formula: ##STR8## whereinRf is a perfluoroalkyl group having 3 to 21 carbon atoms, and A is analkylene group having 1 to 4 carbon atoms or ##STR9## (wherein R¹ is ahydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R² is analkylene group having 1 to 4 carbon atoms)!,

(B) at least one repeating unit derived from an alkyl (meth)acrylatewhose alkyl group has 1 to 6 carbon atoms, and

(C) a repeating unit derived from styrene.

The present invention provides a stainproofing agent comprising afluorine-containing copolymer, said fluorine-containing copolymercomprising:

(A) at least one repeating unit derived from an OH-- andfluorine-containing fumarate represented by the formula: ##STR10##wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms!, or afluorine-containing fumarate represented by the formula: ##STR11##wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, and Ais an alkylene group having 1 to 4 carbon atoms or ##STR12## (wherein R¹is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R²is an alkylene group having 1 to 4 carbon atoms)!,

(B) at least one repeating unit derived from an alkyl (meth)acrylatewhose alkyl group has 1 to 6 carbon atoms, and

(C) a repeating unit derived from styrene.

In the present invention, it is preferred that the repeating unit (A) isan OH-- and fluorine-containing maleate represented by the formula:##STR13## wherein Rf is a perfluoroalkyl group having 3 to 21 carbonatoms!, or an OH-- and fluorine-containing fumarate represented by theformula: ##STR14## wherein Rf is a perfluoroalkyl group having 3 to 21carbon atoms!. The reason why it is preferred to have the OH group isnot clear, but it is assumed that properties of adhesion to a substrateare improved by having the OH group, thereby improving the stainproofproperties and oil repellency.

The present invention provides an OH-- and fluorine-containing maleaterepresented by the formula: ##STR15## wherein Rf is a perfluoroalkylgroup having 3 to 21 carbon atoms!, and an OH-- and fluorine-containingfumarate represented by the formula: ##STR16## wherein Rf is aperfluoroalkyl group having 3 to 21 carbon atoms!.

The present invention also provide a fluorine-containing copolymerhaving a molecular weight of 1000 to 1000000, comprising:

(A) a repeating unit derived from the above fluorine-containing maleateor fumarate which has an OH group or no OH group, and

(B) at least one repeating unit derived from an alkyl (meth)acrylatewhose alkyl group has 1 to 6 carbon atoms,

a weight ratio of the repeating unit (A) to the repeating unit (B) beingfrom 95:5 to 5:95.

The copolymer of the present invention is obtained by polymerizing (A)at least one monomer selected from the fluorine-containing monomers (I)to (IV) with (B) the alkyl (meth)acrylate whose alkyl group has 1 to 6carbon atoms (hereinafter referred to as a "lower alkyl (meth)acrylate")and, if necessary, (C) styrene. The polymerization may be any one of asolution polymerization, an emulsion polymerization and a suspensionpolymerization.

A copolymer may have a repeating unit represented by the formula:##STR17## wherein Rf and A are as defined above! by cleaving acarbon-carbon double bond in the monomer (A).

A repeating unit represented by the formula: ##STR18## wherein R^(1') ishydrogen or a methyl group, and R^(2') is an alkyl group having 1 to 6carbon atoms! is derived by cleaving a carbon-carbon double bond in themonomer (B).

A repeating unit represented by the formula: ##STR19## is derived bycleaving a carbon-carbon double bond in the monomer (C).

The monomer (A) has low solubility in a normal solvent because both endshave a perfluoroalkyl group, but the monomer (A) is soluble in loweralkyl (meth)acrylate (B) and styrene (C). A stable emulsion can beobtained by mixing a monomer (A), a lower alkyl (meth)acrylate (B) and,if necessary, styrene (C) to dissolve the monomer (A) and adding waterand an emulsifier to emulsify the mixture (e.g. mechanicalemulsification, etc.), followed by polymerizing. When using solvents inwhich the monomers (A) to (C) are soluble (e.g. ketone such as methylethyl ketone (MEK), etc.; succinic acid diester such as diethylsuccinate, etc.; chlorine-containing organic solvent such asperchloroethylene, etc.; glycol ethers such asdipropyleneglycolmonomethyl ether, etc.; or glycols such as dipropyleneglycol, etc.), the solution polymerization can be conducted.

The emulsion polymerization may be conducted by polymerizing a monomerin an aqueous medium in the presence of an emulsifier. The aqueousmedium may be water alone, but an organic solvent (e.g. glycol such asdipropylene glycol, etc.; glycol ether such as dipropylene glycolmonomethyl ether, etc.; ketone such as methyl ethyl ketone, etc.; orsuccinic acid diester such as diethyl succinate, etc.) may be containedin an amount of not more than 20% by weight. The emulsifier may be acationic, anionic or nonionic emulsifier. Examples of the emulsifierinclude a cationic emulsifier such as stearyltrimethylammonium chloride,etc.; an anionic emulsifier such as sodium laurylsulfate, etc.; and anonionic emulsifier such as polyoxyethylenealkylphenyl ether, etc. Inorder to initiate the polymerization, a polymerization initiator isused. Examples of the polymerization initiator includeazobisisobutyronitrile, azobis(2-amidinopropane) dihydrochloride,ammonium persulfate, etc. The polymerization temperature is usually from60° to 80° C. The polymerization time usually depends on thepolymerization temperature, and is usually from 5 to 20 hours.

In the copolymer containing no styrene, the weight ratio of the monomer(A) to the alkyl (meth)acrylate having 1 to 6 carbon atoms (B) isusually from 95/5 to 5/95, preferably from 80/20 to 10/90, morepreferably from 70/30 to 15/85, further preferably from 70/30 to 40/60.When the ratio of the monomer (A) is less than 5% by weight, the oilrepellency is liable to be lowered. When the ratio of the monomer (B) isless than 5% by weight, the stainproof properties are liable to belowered.

In the copolymer containing styrene, the weight ratio of the monomer(A)/the alkyl (meth)acrylate having 1 to 6 carbon atoms (B)/styrene (C)is usually from 95-5/balance (5 or more)/0-95, preferably80-10/20-90/1-50, more preferably 70-15/30-85/1-35, further preferablyfrom 65-30/30-65/1-35. When the ratio of the monomer (A) is less than 5%by weight, the oil repellency is liable to be lowered. When the ratio ofthe monomer (A) exceeds 95% by weight, the stainproof properties areliable to be lowered. In addition, when the ratio of styrene exceeds 95%by weight, the oil repellency and stainproof properties are liable to belowered.

The number-average molecular weight (according to gel permeationchromatography (GPC)) of the copolymer of the present invention isusually from 1000 to 1000000, preferably from 50000 to 400000.

The fluorine-containing maleates or fumarates (I) to (IV) are diestersof maleic or fumaric acid. In the fluorine-containing maleates orfumarates (I) to (IV), the number of carbon atoms of a Rf group ispreferably from 6 to 14. The Rf group may be in the branched orstraight-chain form.

The fluorine-containing maleate represented by the formula (I) can beobtained by the following reaction scheme. ##STR20## wherein Rf is asdefined above!.

That is, maleic acid may be reacted with3-perfluoroalkyl-1,2-epoxypropane. It is preferred that this reaction isconducted in a solution dissolved in a solvent in the presence of acatalyst. Examples of the catalyst include an ammonium salt (e.g.trimethylbenzylammonium chloride, etc.) and a tertiary amine (e.g.dimethylbenzylamine, etc.). Examples of the solvent include ketone (e.g.methyl ethyl ketone, methyl isobutyl ketone, etc.); succinic aciddiester such as diethyl succinate, etc.; glycol ethers such asdipropylene glycol monomethyl ether, etc.; and glycols such asdipropylene glycol, etc. The reaction temperature is usually from 80° to120° C. The reaction temperature may be the temperature at which thesolvent is allowed to reflux. The reaction time depends on the reactiontemperature, and is usually from 5 to 20 hours.

The fluorine-containing fumarate represented by the formula (II) can beproduced by replacing maleic acid with fumaric acid in the process forproducing the fluorine-containing maleate represented by the formula(I). That is, the fluorine-containing fumarate (II) can be obtained byreacting fumaric acid with 3-perfluoroalkyl-1,2-epoxypropane. Theconditions for producing the fluorine-containing fumarate (II) are thesame as those for producing the fluorine-containing maleate (I).

The fluorine-containing maleate represented by the formula (III) can beproduced according to the following reaction scheme. ##STR21## whereinRf and A are as defined above!.

It is preferred that this reaction is conducted in a solution dissolvedin a solvent in the presence of a catalyst. Examples of the catalystinclude p-toluenesulfonic acid, sulfuric acid and the like. Examples ofthe solvent include benzene, toluene and the like. The reaction isusually conducted at the reflux temperature of the solvent. The reactiontime depends on the reaction temperature, and is usually from 6 to 12hours.

The fluorine-containing fumarate represented by the formula (IV) can beproduced by replacing maleic acid with fumaric acid in the process forproducing the fluorine-containing maleate represented by the formula(III). That is, the fluorine-containing fumarate (IV) can be obtained byreacting fumaric acid with perfluoroalkyl alcohol. The conditions forproducing the fluorine-containing fumarate (IV) are the same as thosefor producing the fluorine-containing maleate (III).

When the A group in the fluorine-containing maleate (III) andfluorine-containing fumarate (IV) is an alkylene group, the alkylenegroup may be --CH₂ --,--CH₂ CH₂ --,--CH₂ CH₂ CH₂ --,--CH₂ CH₂ CH₂ CH₂--, ##STR22## and the like.

In the lower alkyl (meth)acrylate (B), the number of carbon atoms of alower alkyl group is preferably from 1 to 6. Examples of the lower alkylgroup include methyl group, ethyl group, n-propyl group, iso-propylgroup, n-butyl group, iso-butyl group, t-butyl group, n-pentyl group,cyclopentyl group, n-hexyl group, cyclohexyl group and the like.

The lower alkyl (meth)acrylate (B) used in the copolymer may be amixture of methyl (meth)acrylate and a C₂ -C₆ alkyl (meth)acrylate (e.g.ethyl (meth)acrylate, butyl (meth)acrylate, etc.).

One of the lower alkyl (meth)acrylates dissolves the monomer (A), butthe solubility of the monomer (A) is further improved by using two ofthem. Specifically, a combination of methyl methacrylate (MMA) and ethylmethacrylate (EMA) is preferred.

The molar ratio of the methyl (meth)acrylate to the C₂ -C₆ alkyl(meth)acrylate may be preferably from 100:0 to 0:100, more preferablyfrom 80:20 to 50:50.

In the stainproofing agent of the present invention, it is also possibleto copolymerize with the other polymerizable monomer. Examples of theother polymerizable monomer include vinyl acetate, vinyl chloride,vinylidene chloride, acrylic acid and an alkyl ester thereof,methacrylic acid and an alkyl ester thereof, vinyl alkyl ether,halogenated alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene,chloroprene, benzyl acrylate, benzyl (meth)acrylate, maleic anhydride,acrylamide, methacrylamide, diacetonacrylamide, N-methylol acrylamide,N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate,3-chloro-2-hydroxypropyl methacrylate, glycidyl acrylate, glycidylmethacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, blockedisocyanate group-containing (meth)acrylate, urethane linkage-containingpoly(meth)acrylate and the like.

It is also possible to copolymerize with a perfluoroalkylgroup-containing (meth)acrylate.

The stainproofing agent of the present invention comprises a copolymerand a medium. The medium may be any solvent such as water and organicsolvent (e.g. alcohol, ester, ketone, glycol, glycol ethers, etc.). Inthe stainproofing agent, the amount of the copolymer is usually from 15to 40% by weight.

The stainproofing agent of the present invention can be applied by anymethod according to the kind of the material to be treated. For example,there can be used a method of applying a copolymer on the surface of amaterial to be treated, using a known application procedure such asimmersion, coating, etc., followed by drying. If necessary, the curingmay be conducted by applying together with a suitable crosslinkingagent. Furthermore, the stainproofing agent of the present invention maybe mixed with the other polymer, e.g. polymethyl methacrylate/ethylmethacrylate (P-MMA/EMA) emulsion. Other water repellents, oilrepellents, and additives such as insect repellents, flame retardants,antistatic agents, softeners, wrinkle inhibitors, etc. may beappropriately added. In case of immersion, the concentration of thecopolymer in the immersion solution is normally from 0.05 to 10% byweight. In case of coating, the concentration of the copolymer in thecoating solution is usually from 0.1 to 5% by weight.

The material to be treated with the stainproofing agent of the presentinvention is preferably a textile, and a carpet is particularlypreferred. Examples of the textile include animal- or vegetable-originnatural fibers such as cotton, hemp, wool, silk, etc.; synthetic fiberssuch as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile,polyvinyl chloride, polypropylene, etc.; semisynthetic fibers such asrayon, acetate, etc.; inorganic fibers such as glass fibers, carbonfibers, asbestos fibers, etc.; and a mixture of these fibers. Thetextile may be in any form such as a fiber, a yarn, a cloth and thelike. When a carpet is treated with the stainproofing agent of thepresent invention, the carpet may be formed after treating fibers oryarns with the stainproofing agent. Alternatively, the formed carpet maybe treated with the stainproofing agent. Examples of the material to betreated with the stainproofing agent of the present invention includeglass, paper, wood, hide, fur, asbestos, brick, cement, metal and oxide,ceramic, plastic, coated surface and plaster, in addition to thetextile.

PREFERRED EMBODIMENT OF THE INVENTION

The present invention will be illustrated by the following Exampleswhich do not limit the present invention.

The stainproofing agents obtained in the Examples and ComparativeExamples were evaluated as follows.

Each emulsion obtained in the Examples and Comparative Examples isdiluted with water to prepare a solution containing a solid content of3% by weight, which is a treating solution. This treating solution isspray-coated on a nylon loop-pile carpet fabric (non-backed product) sothat a coating weight is 100 g/m², followed by drying with heating at130° C. for 3 minutes. The treated carpet is subjected to tests of thewater repellency, oil repellency and dry soiling stainproof properties.

1) Water repellency

The water repellency is determined by gently dropping small drops of anisopropyl alcohol/water mixed solution having the following compositionon the surface of a carpet fabric and measuring a maximum content ofisopropyl alcohol in the solution which maintains a shape of the dropafter 3 minutes.

    ______________________________________                                        Mixing composition (volume ratio, %)                                          Isopropyl alcohol                                                                             Water                                                         ______________________________________                                        50              50                                                            40              60                                                            30              70                                                            20              80                                                            10              90                                                             0              100                                                           ______________________________________                                    

2) Oil repellency

The oil repellency is determined according to AATCC-TM-118-1966 bydropping several drops (diameter: about 4 mm) of the following testsolution on two positions of the surface of a test cloth, observing thepenetration state of the drops after 30 seconds and measuring a maximumpoint of the oil repellency given by the test solution which does notpenetrate.

    ______________________________________                                                                   Surface tension                                    Oil repellency                                                                           Test solution   (dyn/cm, 25° C.)                            ______________________________________                                        8          n-Heptane       20.0                                               7          n-Octane        21.8                                               6          n-Decane        23.5                                               5          n-Dodecane      25.0                                               4          n-Tetradecane   26.7                                               3          n-Hexadecane    27.3                                               2          n-Hexadecane 35 by weight                                                                     29.6                                                          Nujol 65 by weight                                                 1          Nujol           31.2                                               0          Inferior to 1   --                                                 ______________________________________                                    

3) Stainproof properties

First, a carpet is contaminated with a dry soil having the followingcomposition according to JIS L 1023-1992.

    ______________________________________                                        Component             Weight ratio (%)                                        ______________________________________                                        Peat moss                 40                                                  Portland cement (JIS R 5210)                                                                            17                                                  White clay      (JIS K 8746)                                                                            17                                                  Diatomaceous earth                                                                            (JIS K 8330)                                                                            17                                                  Carbon black    (JIS K 5107)                                                                            0.1                                                 Iron oxide (III) for ferrite                                                                  (JIS K 1462)                                                                            0.15                                                Nujol                     8.75                                                ______________________________________                                    

After the excess dry soil on the surface is sucked with a cleaner,brightness of the surface is measured by a calorimeter and a stainingdegree is calculated onthe basis of the following equation, which istaken for evaluation of dry soil stainproof properties.

    Staining degree(%)= (L.sub.0 -L)/L.sub.0 !×100

(wherein L₀ : brightness before contamination,

L: brightness after contamination).

Synthesis Example 1

(Synthesis of Rf(OH) maleate)

3-Perfluoroalkyl (a mixture wherein a molar ratio of C₆ F₁₃, C₈ F₁₇, C₁₀F₂₁, C₁₂ F₂₅ and C₁₄ F₂₉ (=Rf) is 2:50:30:15:3, average molecularweight: 528)-1,2-epoxypropane (317 g, 0.600 mol) was dissolved in 200 gof methyl ethyl ketone (MEK), followed by heating to 80° C. After maleicacid (35.4 g, 0.305 mol) was added and sufficiently dissolved, 2.2 g oftrimethylbenzylammonium chloride was added as a catalyst. The reactionwas conducted in a reflux state for 20 hours. Then, contents were pouredinto a large amount of methanol to obtain 321 g of a precipitate (Rf(OH)maleate) (yield: 92%).

It was confirmed by a mass spectrometry and a gas chromatography that aconversion of 3-perfluoroalkyl-1,2-epoxypropane is 100% and a new peakindicates bis-3-perfluoroalkyl-2-hydroxy-propyl maleate as a product. AnIR chart of the product is shown in FIG. 1.

Synthesis Example 2

(Synthesis of Rf(OH) fumarate)

The same manner as in Synthesis Example 1 was repeated, except for using35.4 g of fumaric acid in place of maleic acid, to give a Rf(OH)fumarate. An IR chart of the product is shown in FIG. 2.

Synthesis Example 3

(Synthesis of Rf maleate)

This example illustrates the preparation of the fluorine-containingmaleate (III) wherein A is --CH₂ CH₂ --.

Perfluoroalkylethanol RfCH₂ CH₂ OH (a mixture wherein a molar ratio ofC₆ F₁₃, C₈ F₁₇, C₁₀ F₂₁, C₁₂ F₂₅ and C₁₄ F₂₉ (=Rf) is 2:50:30:15:3,average molecular weight: 516)! (300 g, 0.581 mol), maleic acid (132 g,1.138 mol) and 80 g of benzene were charged in a flask equipped with adean-stalk trap, followed by heating to 55° C. with stirring. After 0.1g of p-toluenesulfonioc acid and 0.4 g of sulfuric acid were added, andthe mixture was heated to 83° C. The reaction was continuously conductedunder reflux of benzene with removing water for 11 hours. After 28 g ofan aqueous 10% sodium carbonate solution was added, the reactionsolution was continuously stirred for 2 hours, and benzene and waterwere distilled off at 88° C. under 20 mmHg. The temperature was raisedto about 90° C., an insoluble material was removed by filtering thesolution through a SUS mesh to obtain 400 g of a Rf maleate (yield:93%).

Synthesis Example 4

(Synthesis of Rf fumarate)

The same manner as in Synthesis Example 3 was repeated, except for using132 g of fumaric acid in place of maleic acid, to prepare a fluorine-containing fumarate (IV) wherein A is --CH₂ CH₂ --.

EXAMPLE 1

120 g of Rf(OH) maleate was sufficiently dissolved in 280 g of methylmethacrylate. Then 25 g of sodium α-olefinsulfonate, 28 g of Tween 80(polyoxyethylenesorbitan monooleate), 0.1 g of laurylmercaptane and 684g of deionized water were added and the mixture was emulsified using ahigh-pressure homogenizer. The resulting emulsion was charged in a 2liter four-necked flask equipped with a reflux condenser, a nitrogenintroducing tube, a thermometer and a stirring device, and thenmaintained at 60° C. under a nitrogen flow for about one hour. Ammoniumpersulfate (1.1 g) dissolved in 5 g of water was added to initiate thepolymerization, followed by heating with stirring at 60° C. for 8 hours.The solid content of the resulting polymer emulsion was 40%.

The polymer has the composition shown in Table I.

The water repellency, oil repellency and stainproof properties wereevaluated. The results are shown in Table I.

EXAMPLES 2 to 8

The same manner as in Example 1 was repeated, except for using themonomers shown in Table I, to prepare a copolymer. The copolymer has thecomposition shown in Table I.

The results of the water repellency, oil repellency and stainproofproperties are shown in Table I.

EXAMPLES 9

120 g of Rf(OH) maleate was sufficiently dissolved in 120 g of methylmethacrylate, 120 g of ethyl methacrylate and 40 g of styrene. Then 28 gof sodium α-olefinsulfonate, 28 g of Tween 80 (polyoxyethylenesorbitanmonooleate), 0.1 g of laurylmercaptane and 684 g of deionized water wereadded and the mixture was emulsified using a high-pressure homogenizer.The resulting emulsion was charged in a 2 liter four-necked flaskequipped with a reflux condenser, a nitrogen introducing tube, athermometer and a stirring device, and then maintained at 60° C. under anitrogen flow for about one hour. Ammonium persulfate (1.1 g) dissolvedin 5 g of water was added to initiate the polymerization, followed byheating with stirring at 60° C. for 8 hours. The solid content of theresulting polymer emulsion was 40%.

The polymer has the composition shown in Table I.

The results of the water repellency, oil repellency and stainproofproperties are shown in Table I.

EXAMPLES 10 to 48 and Comparative Examples 1 to 16

The same manner as in Example 9 was repeated, except for using themonomers shown in Table I, to prepare a copolymer. The copolymer has thecomposition shown in Table I.

The results of the water repellency, oil repellency and stainproofproperties are shown in Table I.

                                      TABLE I                                     __________________________________________________________________________                       Molecular                                                  Example                                                                            Composition of polymer                                                                      weight                                                                             Water                                                                              Oil  Stainproof                                  No.  (weight ratio)                                                                              (Mn) repellency                                                                         repellency                                                                         properties                                  __________________________________________________________________________     1   Rf maleate/MMA (30/70)                                                                      250000                                                                             20   4    21                                           2   Rf maleate/MMA/Sty                                                                          200000                                                                             20   5    19                                               (30/60/10)                                                                3   Rf maleate/MMA/EMA                                                                          160000                                                                             20   5    20                                               (30/35/35)                                                                4   Rf maleate/MMA/EMA/Sty                                                                      160000                                                                             20   5    18                                               (30/30/30/10)                                                             5   Rf maleate/MMA/BMA/Sty                                                                      140000                                                                             20   5    19                                               (30/30/30/10)                                                             6   Rf (OH) maleate/MMA (30/70)                                                                 150000                                                                             30   5    19                                           7   Rf (OH) maleate/MMA/Sty                                                                     150000                                                                             30   6    17                                               (30/60/10)                                                                8   Rf (OH) maleate/MMA/EMA                                                                     150000                                                                             30   6    17                                               (30/35/35)                                                                9   Rf (OH) maleate/MMA/                                                                        160000                                                                             30   6    15                                               EMA/Sty (30/30/30/10)                                                    10   Rf (OH) maleate/MMA/BMA/                                                                    160000                                                                             30   6    18                                               Sty (30/30/30/10)                                                        11   Rf (OH) maleate/EMA (30/70)                                                                 140000                                                                             30   5    20                                          12   Rf (OH) maleate/EMA/Sty                                                                     160000                                                                             30   5    19                                               (30/35/35)                                                               13   Rf (OH) maleate/MMA/EMA                                                                      80000                                                                             30   5    18                                               (50/25/25)                                                               14   Rf (OH) maleate/MMA/EMA/                                                                     80000                                                                             40   6    16                                               Sty (50/20/20/10)                                                        15   Rf (OH) maleate/MMA/EMA                                                                      60000                                                                             40   6    19                                               (70/15/15)                                                               16   Rf (OH) maleate/MMA/EMA/                                                                     60000                                                                             40   6    19                                               Sty (70/12.5/12.5/5)                                                     17   Rf fumarate/MMA (30/70)                                                                     300000                                                                             20   4    25                                          18   Rf fumarate/MMA/Sty                                                                         350000                                                                             20   4    23                                               (30/60/10)                                                               19   Rf fumarate/MMA/EMA                                                                         170000                                                                             20   4    24                                               (30/35/35)                                                               20   Rf fumarate/MMA/EMA/Sty                                                                     190000                                                                             20   4    22                                               (30/30/30/10)                                                            21   Rf fumarate/MMA/BMA/Sty                                                                     170000                                                                             20   4    23                                               (30/30/30/10)                                                            22   Rf (OH) fumarate/MMA(30/70)                                                                 170000                                                                             20   5    21                                          23   Rf (OH) fumarate/MMA/Sty                                                                    180000                                                                             20   5    20                                               (30/60/10)                                                               24   Rf (OH) fumarate/MMN/EMA                                                                    170000                                                                             20   5    20                                               (30/35/35)                                                               25   Rf (OH) fumarate/MMN/EMA/                                                                   180000                                                                             20   5    18                                               Sty (30/30/30/10)                                                        26   Rf (OH) fumarate/MMA/                                                                       180000                                                                             20   5    19                                               BMA/Sty (30/30/30/10)                                                    27   Rf (OH) fumarate/MMA/EMA                                                                    100000                                                                             20   5    20                                               (50/25/25)                                                               28   Rf (OH) fumarate/MMA/EMA/                                                                   100000                                                                             20   5    18                                               Sty (50/20/20/10)                                                        29   Rf (OH) fumarate/MMA/EMA                                                                     60000                                                                             20   5    19                                               (70/15/15)                                                               30   Rf (OH) fumarate/MMA/EMA/                                                                    60000                                                                             20   5    18                                               Sty (70/12.5/12.5/5)                                                     31   Rf (OH) maleate/MMA/StA/                                                                    140000                                                                             30   6    19                                               (30/60/10)                                                               32   Rf (OH) maleate/MMA/EMA/                                                                    140000                                                                             30   6    20                                               StA (30/30/30/10)                                                        33   Rf (OH) maleate/MA (30/70)                                                                  200000                                                                             30   5    19                                          34   Rf (OH) maleate/MA/EA                                                                       200000                                                                             30   5    19                                               (30/35/35)                                                               35   Rf (OH) maleate/MMA/EA                                                                      200000                                                                             30   5    18                                               (30/35/35)                                                               36   Rf (OH) maleate/MA/EMA                                                                      200000                                                                             30   5    18                                               (30/35/35)                                                               37   Rf (OH) maleate/MMA/CHMA                                                                    150000                                                                             30   6    17                                               (30/35/35)                                                               38   Rf (OH) maleate/MMA/EMA/                                                                    180000                                                                             30   6    16                                               CHMA (30/30/30/10)                                                       39    Rf (OH) maleate/MMA/EMA/                                                                   400000                                                                             30   6    15                                               Sty (70/12.5/12.5/5)                                                          + P-MMA/EMA (80/20)!                                                          (50 + 50)                                                                40    Rf (OH) maleate/MMA/EMA/                                                                   400000                                                                             40   5    17                                               Sty (30/30/30/10)                                                             + Water and oil repellent!                                                    (90 + 10)                                                                41   BrRf maleate/MMA/EMA/Sty                                                                    100000                                                                             20   5    18                                               (30/30/30/10)                                                            42   BrRf (OH)     100000                                                                             30   6    15                                               maleate/MMA/EMA/Sty                                                           (30/30/30/10)                                                            43   BrRf fumarate/MMA/EMA/Sty                                                                   200000                                                                             20   4    22                                               (30/30/30/10)                                                            44   BrRf (OH) fumarate/                                                                         200000                                                                             20   5    18                                               MMA/EMA/ Sty (30/30/30/10)                                               45   C.sub.8 F.sub.17 SA maleate/MMA/EMA/                                                        200000                                                                             20   5    18                                               Sty (30/30/30/10)                                                        46   C.sub.8 F.sub.17 SA fumarate/MMA/EMA/                                                       300000                                                                             20   4    22                                               Sty (30/30/30/10)                                                        47   Rf maleate/MMA                                                                               60000                                                                             20   4    25                                          48   C.sub.8 F.sub.17 SA (H)                                                                     190000                                                                             20   5    18                                               maleate/MMA/EMA/Sty                                                      __________________________________________________________________________    Comparative             Water                                                                              Oil  Stainproof                                  Example No.                                                                         Composition of polymer (weight ratio)                                                           repellency                                                                         repellency                                                                         properties                                  __________________________________________________________________________    Comparative                                                                         Rf maleate Homopolymer (100)                                                                    20   4    30                                          example 1                                                                     Comparative                                                                         Rf fumarate Homopolymer (100)                                                                   10   3    32                                          example 2                                                                     Comparative                                                                         MeRf maleate Homopolymer (100)                                                                  10   1    34                                          example 3                                                                     Comparative                                                                         MeRf maleate/MMA (70/30)                                                                         0   0    30                                          example 4                                                                     Comparative                                                                         MeRf maleate/Sty (70/30)                                                                         0   0    29                                          example 5                                                                     Comparative                                                                         MeRf maleate/MMA/Sty (70/15/15)                                                                  0   1    29                                          example 6                                                                     Comparative                                                                         MeRf maleate/MMA (30/70)                                                                         0   0    28                                          example 7                                                                     Comparative                                                                         MeRf maleate/Sty (30/70)                                                                         0   0    28                                          example 8                                                                     Comparative                                                                         MeRf maleate/MMA/Sty (70/15/15)                                                                 10   1    30                                          example 9                                                                     Comparative                                                                         MeC.sub.8 F.sub.17 SA maleate Homopolymer                                                       10   1    30                                          example 10                                                                          (100)                                                                   Comparative                                                                         MeC.sub.8 F.sub.17 SA maleate/MMA (30/70)                                                        0   0    28                                          example 11                                                                    Comparative                                                                         iPrC.sub.8 F.sub.17 fumarate/VPiv (90/10)                                                       20   1    30                                          example 12                                                                    Comparative                                                                         Rf itaconate/MMA (30/70)                                                                        20   2    27                                          example 13                                                                    Comparative                                                                         MeC.sub.8 F.sub.17 SA maleate/C.sub.8 F.sub.17 SA                                                0   0    28                                          example 14                                                                          maleate/MMA (21/9/70)                                                   Comparative                                                                         BuC.sub.8 F.sub.17 SA maleate/VAc (68/32)                                                        0   0    31                                          example 15                                                                    Comparative                                                                         EtC.sub.8 F.sub.17 SA maleate/VPr/GMA (78/20/2)                                                  0   0    31                                          example 16                                                                    __________________________________________________________________________

Note)

Rf maleate: ##STR23## (Mixture wherein a molar ratio of C₆ F₁₃, C₈ F₁₇,C₁₀ F₂₁, C₁₂ F₂₅ and C₁₄ F₂₉ (=Rf) is 2:50:30:15:3)

Rf fumarate: ##STR24## (Mixture wherein a molar ratio of C₆ F₁₃, C₈ F₁₇,C₁₀ F₂₁, C₁₂ F₂₅ and C₁₄ F₂₉ (=Rf) is 2:50:30:15:3)

Rf(OH) maleate: ##STR25## (Mixture wherein a molar ratio of C₆ F₁₃, C₈F₁₇, C₁₀ F₂₁, C₁₂ F₂₅ and C₁₄ F₂₉ (=Rf) is 2:50:30:15:3)

Rf(OH) fumarate: ##STR26## (Mixture wherein a molar ratio of C₆ F₁₃, C₈F₁₇, C₁₀ F₂₁, C₁₂ F₂₅ and C₁₄ F₂₉ (=Rf) is 2:50:30:15:3)

MMA: Methyl methacrylate

Sty: Styrene

EMA: Ethyl methacrylate

BMA: Butyl methacrylate

StA: Stearyl acrylate

MA: Methyl acrylate

EA: Ethyl acrylate

CHMA: Cyclohexyl methacrylate

Water and oil repellent: TG-452A (manufactured by Daikin IndustriesLtd.)

BrRf maleate: ##STR27## (Mixture wherein a molar ratio of C₇ F₁₅, C₉F₁₉, C₁₁ F₂₃, C₁₃ F₂₇ and C₁₅ F₃₁ (=Rf) is 2:50:30:15:3)

BrRf fumarate: ##STR28## (Mixture wherein a molar ratio of C₇ F₁₅, C₉F₁₉, C₁₁ F₂₃, C₁₃ F₂₇ and C₁₅ F₃₁ (=Rf) is 2:50:30:15:3)

BrRf(OH) maleate: ##STR29## (Mixture wherein a molar ratio of C₇ F₁₅, C₉F₁₉, C₁₁ F₂₃, C₁₃ F₂₇ and C₁₅ F₃₁ (=Rf) is 2:50:30:15:3)

BrRf(OH) fumarate: ##STR30## (Mixture wherein a molar ratio of C₇ F₁₅,C₉ F₁₉, C₁₁ F₂₃, C₁₃ F₂₇ and C₁₅ F₃₁ (=Rf) is 2:50:30:15:3)

C₈ F₁₇ SA maleate: ##STR31## C₈ F₁₇ SA fumarate: Trans-form of C₈ F₁₇ SAmaleate C₈ F₁₇ SA(H) maleate: ##STR32## MeRf maleate: ##STR33## (Mixturewherein a molar ratio of C₆ F₁₇, C₈ F₁₇, C₁₀ F₂₁, C₁₂ F₂₅ and C₁₄ F₂₉(=Rf) is 2:50:30:15:3)

MeC₈ F₁₇ SA maleate: ##STR34## iPrC₈ F₁₇ fumarate: ##STR35## VPiv: Vinylpivalate Rf itaconate: ##STR36## BuC₈ F₁₇ SA maleate: ##STR37## VAc:Vinyl acetate EtC₈ F₁₇ SA maleate: ##STR38## VPr: Vinyl propionate GMA:Glycidyl methacrylate

EFFECT OF THE INVENTION

The stainproofing agent of the present has excellent water repellency,oil repellency and stainproof properties which have never beenheretofore obtained.

We claim:
 1. A stainproofing agent comprising a fluorine-containingcopolymer, said fluorine-containing copolymer comprising:(A) at leastone repeating unit derived from a monomer which is selected from thegroup consisting of an OH--and fluorine-containing maleate representedby the formula: ##STR39## wherein Rf is a perfluoroalkyl group having 3to 21 carbon atoms, an OH--and fluorine-containing fumarate representedby the formula: ##STR40## wherein Rf is a perfluoroalkyl group having 3to 21 carbon atoms, a fluorine-containing maleate represented by theformula: ##STR41## wherein Rf is a perfluoroalkyl group having 3 to 21carbon atoms, and A is an alkylene group having 1 to 4 carbon atoms or##STR42## wherein R¹ is a hydrogen atom or an alkyl group having 1 to 4carbon atoms, and R² is an alkylene group having 1 to 4 carbon atoms,and a fluorine-containing fumarate represented by the formula: ##STR43##wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, and Ais an alkylene group having 1 to 4 carbon atoms or ##STR44## wherein R¹is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R²is an alkylene group having 1 to 4 carbon atoms; and (B) at least onerepeating unit derived from an alkyl (meth)acrylate whose alkyl grouphas 1 to 6 carbon atoms.
 2. A stainproofing agent comprising afluorine-containing copolymer, said fluorine-containing copolymercomprising:(A) at least one repeating unit derived from an OH--andfluorine-containing maleate represented by the formula: ##STR45##wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, or afluorine-containing maleate represented by the formula: ##STR46##wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, and Ais an alkylene group having 1 to 4 carbon atoms or ##STR47## wherein R¹is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R²is an alkylene group having 1 to 4 carbon atoms, (B) at least onerepeating unit derived from an alkyl (meth)acrylate whose alkyl grouphas 1 to 6 carbon atoms, and (C) a repeating unit derived from styrene.3. A stainproofing agent comprising an OH--and fluorine-containingcopolymer, said fluorine-containing copolymer comprising:(A) at leastone repeating unit derived from an OH--and fluorine- containing fumaraterepresented by the formula: ##STR48## wherein Rf is a perfluoroalkylgroup having 3 to 21 carbon atoms, or a fluorine-containing fumaraterepresented by the formula: ##STR49## wherein Rf is a perfluoroalkylgroup having 3 to 21 carbon atoms, and A is an alkylene group having 1to 4 carbon atoms or ##STR50## wherein R¹ is a hydrogen atom or an alkylgroup having 1 to 4 carbon atoms, and R² is an alkylene group having 1to 4 carbon atoms, (B) at least one repeating unit derived from an alkyl(meth)acrylate whose alkyl group has 1 to 6 carbon atoms; and (C) arepeating unit derived from styrene.
 4. A stainproofing agent comprisinga fluorine-containing copolymer, said fluorine-containing copolymercomprising:(A) at least one repeating unit derived from a monomer whichis selected from an OH--and fluorine-containing maleate represented bythe formula: ##STR51## wherein Rf is a perfluoroalkyl group having 3 to21 carbon atoms, an OH--and fluorine-containing fumarate represented bythe formula: ##STR52## wherein Rf is a perfluoroalkyl group having 3 to21 carbon atoms, a fluorine-containing maleate represented by theformula: ##STR53## wherein Rf is a perfluoroalkyl group having 3 to 21carbon atoms, and A is an alkylene group having 1 to 4 carbon atoms or##STR54## wherein R¹ is a hydrogen atom or an alkyl group having 1 to 4carbon atoms, and R² is an alkylene group having 1 to 4 carbon atoms, ora fluorine-containing fumarate represented by the formula: ##STR55##wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms, and Ais an alkylene group having 1 to 4 carbon atoms or ##STR56## wherein R¹is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R²is an alkylene group having 1 to 4 carbon atoms, (B) two repeating unitsderived from an alkyl (meth)acrylate whose alkyl group has 1 to 6 carbonatoms, and (C) a repeating unit derived from styrene.
 5. Thestainproofing agent according to any one of claims 1 to 4, wherein therepeating unit (A) is derived from an OH--and fluorine-containingmaleate represented by the formula: ##STR57## wherein Rf is aperfluoroalkyl group having 3 to 21 carbon atoms, or an OH--andfluorine-containing fumarate represented by the formula: ##STR58##wherein Rf is a perfluoroalkyl group having 3 to 21 carbon atoms.
 6. Thestainproofing agent according to claim 1, the repeating unit (B) isderived from an alkyl (meth)acrylate whose alkyl group has 1 to 3 carbonatoms.